Non-opaque flame retardant polycarbonate composition

ABSTRACT

A non-opaque flame retardant polycarbonate composition comprising in admixture an aromatic carbonate polymer and an additive which may be the metal salts of either monomeric or polymeric aromatic ether sulfonic acids; said aromatic carbonate polymer and additive having a refractive index in the range of 1.54 to 1.65.

This invention is directed to a non-opaque flame retardant polycarbonatecomposition and in particular an aromatic polycarbonate containing inadmixture therewith an additive which may be the metal salts of sulfonicacids of aromatic ethers and mixtures thereof, wherein said aromaticpolycarbonate and additive have a refractive index in the range of 1.54to 1.65 and articles therefrom.

BACKGROUND OF THE INVENTION

With the increasing concern for safety, there is a positive move towardproviding safe materials for public and household use. One particulararea of need is that of providing flame resistant or flame retardantnon-opaque products for use by the ultimate consumer. As a result ofthis demand, many products are being required to meet certain flameretardant criteria both by local and federal government and themanufacturers of such products. One particular set of conditionsemployed as a measuring standard for flame retardancy is set forth inUnderwriter's Laboratories, Inc. Bulletin 94. This Bulletin sets forthcertain conditions by which materials are rated for self-extinguishingcharacteristics.

In the art, there are many known flame retardant additives which areemployed by mixing with products to render such materialsself-extinguishing or flame retardant. Such flame retardant additiveshave been known to be employed in amounts of 5 to 20 weight percent inorder to be effective in extinguishing burning of those products whichare combustible. It has also been found that such amounts can have adegrading effect upon the base product to be rendered flame retardant,resulting in the losses of valuable physical properties of the baseproduct. This is particularly so when employing known flame retardantadditives with the base product polycarbonate resins. Many of theseknown additives have a degrading effect upon the polymer.

In many instances, it is desirable that articles produced from thesefire retardant polycarbonate resins retain their non-opaquecharacteristics.

From U.S. Pat. No. 3,953,396 to Victor Mark issued Apr. 27, 1976, flameretardant polycarbonate compositions comprising in admixture, anaromatic carbonate polymer and a flame retardant additive which may bethe metal salts of sulfonic acids of aromatic ethers is disclosed.

DESCRIPTION OF THE INVENTION

It has now been surprisingly discovered that an aromatic polycarbonatecan be made flame retardant while retaining its non-opaquecharacteristics by incorporating with the aromatic polycarbonate 0.001to about 2.0 parts per hundred parts of aromatic polycarbonate ofcertain additives, which additives are inert, do not degrade thearomatic polycarbonate and also retain the non-opaque characteristics ofthe polycarbonate composition.

The shaped article of the present invention is that comprising anaromatic carbonate polymer and from 0.001 to about 2.0 parts per hundredparts of aromatic carbonate polymer of an additive selected from thegroup consisting of the metal salts of substituted and unsubstitutedsulfonic acids of aromatic ethers, and mixtures thereof, wherein saidmetal salts are selected from the group consisting of alkali metals andalkaline earth metals, and mixtures of these metal salts, and saidsubstituent on the metal salt of the substituted sulfonic acids ofaromatic ethers is selected from the group consisting of alkyl, aryl,alkoxy, aryloxy of 1 to 12 carbon atoms and electron withdrawingradicals and mixtures of these wherein the shaped article has arefractive index in the range of 1.54 to 1.65. Particularly preferredshaped articles are in the form of a sheet and a pellet.

The refractive indices of the materials herein are determined by theimmersion method as described in Physical Methods of Organic Chemistry,by Arnold Weissberger, Interscience Publishers, Volume II, 1960 (page1433).

When the refractive index of the instant additives is in the range ofthe refractive index of the aromatic carbonate polymer, i.e., 1.54 to1.65, the polycarbonate composition and shaped article producedtherefrom is non-opaque. This means that it is able to transmit lightand is from translucent to transparent. Depending upon how close therefractive index of the additive is to that of the polycarbonate, thiswill determine whether the resulting composition is transparent ortranslucent. If the additive at the concentration employed is partiallyor totally soluble in the polycarbonate polymer, the more transparentthe composition and resulting article will be.

More specifically, the particular additive of this invention is themetal salt of substituted and unsubstituted sulfonic acids of aromaticethers and mixtures thereof. The metal salt employed in the practice ofthis invention is either the alkali metal or alkaline earth metal saltor mixtures of these metal salts. The metals of these groups are sodium,lithium, potassium, rubidium, cesium, beryllium, magnesium, calcium,strontium and barium.

The sulfonic acids of aromatic ethers employed in the practice of thisinvention are substituted or unsubstituted sulfonic acids of aromaticethers wherein the substituent consists of alkyl, aryl, alkoxy, andaryloxy of 1-12 carbon atoms or an electron withdrawing radical andmixtures thereof. As employed herein and within the scope of thisinvention, any of the electron withdrawing radicals can be employed inthe practice of this invention. However, preferably, the electronwithdrawing radical or substituent employed in the practice of thisinvention is the halo-, nitro-, trihalomethyl and cyano electronwithdrawing radicals or mixtures of these electron withdrawing radicals.

The electron withdrawing phenomenon, or as it is also referred to aselectronegativity, is defined in Basic Principles of Organic Chemistryby Roberts and Caserio, 1964 (pages 185-186), and Physical OrganicChemistry by Jack Hine, McGraw-Hill Book Company, Inc. 1962 (pages 5, 32and 85-93). Briefly, the electron withdrawing phenomenon is where theradical has a strong affinity for a negative charge, namely electrons,but still remains covalent and does not form an ion. This is anextremely brief description of this phenomenon and is merely set forthhere to describe the electron withdrawing effect. Reference should bemade to the texts set forth above.

In the practice of this invention the metal salt of the sulfonic acid ofaromatic ethers can best be represented by the following formula:

    R'--(O).sub.1-2 -R" (SO.sub.3 M).sub.1-6 (X).sub.0-11      I.

wherein X is independently selected from the group consisting of anelectron withdrawing radical, alkyl, aryl, alkoxy and aryloxy of 1 to 12carbon atoms, M is a metal which may be selected from the periodic tableof either an alkali metal or an alkaline earth metal and R' and R" maybe either an aryl radical of 1-2 aromatic rings or an aliphatic radicalof 1-6 carbon atoms and they may be the same or different. It is to beunderstood, however, that R' and R" together must contain at least onearomatic ring. Also, as shown in the above Formula I, the additive mayor may not have an electron withdrawing radical. For optimum results, itis preferred that the additive contain an electron withdrawing radical,and that both the electron withdrawing radical and the (SO₃ M) radicalbe on the same aromatic ring.

It should also be recognized that in many situations, when preparing thenovel additive of this invention, mixtures of isomeric compositions areobtained. This is due to the various reactive positions on the aromaticring, or rings, as the case may be. Also, mixtures of the various metalsalts of substituted and unsubstituted sulfonic acids of monomericaromatic ethers.

Actually, while there are many compounds that meet the requirements ofFormula I and which offer excellent flame retardant characteristics toan aromatic polycarbonate, the preferred additive employed is potassium4-bromo-diphenylether-4'-sulfonate. This has the following formula:##STR1##

When the polymeric form of the unsubstituted and substituted aromaticether sulfonic acid is employed in the practice of this invention, itcan best be represented by the following formula:

    [A].sub.x [B].sub.y [ArO].sub.n [X].sub.s [SO.sub.3 M].sub.t H

wherein Ar is a phenylene radical, O is oxygen, A is an alkyl radical of1-4 carbons, B is a phenyl radical, X is alkyl, aryl, alkoxy and aryloxyof 1-12 carbon atoms, M is a metal which may be selected from theperiodic table of either an alkali metal or an alkali earth metal, n isan integeer of from 2-300, x, y and s are integers of 0-600 and t is aninteger of 1-600.

While there are many compounds that meet the requirements of Formula IIand which offer excellent flame retardant characteristics to an aromaticpolycarbonate, the preferred additive employed is polysodiumpoly(2,6-dimethylphenyleneoxide) polysulfonate. This has the followingformula: ##STR2## The compositions of the instant invention may containfillers, pigments, dyes, antioxidants, stabilizers, ultraviolet lightabsorbers, mold release agents and other additives commonly employed innon-opaque polycarbonate resin formulations. Furthermore, the shapedarticles may be coated with, for example, mar or scratch-resistantcoatings.

PREFERRED EMBODIMENT OF THE INVENTION

In order to more fully and clearly illustrate the present invention, thefollowing specific examples are presented. It is intended that theexamples be considered as illustrative rather than limiting theinvention disclosed and claimed herein. In the examples, all parts andpercentages are on a weight basis unless otherwise specified.

EXAMPLE 1 100 parts of an aromatic polycarbonate, prepared by reacting2,2-bis(4-hydroxyphenyl)propane and phosgene in the presence of an acidacceptor and a molecular weight regulator and having an intrinsicviscosity of 0.57 is mixed with 0.10 part of a finely ground dehydratedadditive listed in Table I by tumbling the ingredients together in alaboratory tumbler. The resulting mixture is then fed to an extruder,which extruder is operated at about 265° C, and the extrudate iscomminuted into pellets.

The pellets are then injection molded at about 315° C into test bars ofabout 5 in. by 1/2 in. by about 1/16-1/8 in. thick into test squares ofabout 2 in. by 2 in. by about 1/8 in. thick. The test bars (5 for eachadditive listed in the Table) are subject to the test procedure setforth in Underwriters' Laboratories, Inc. Bulletin UL-94, Burning Testfor Classifying Materials. In accordance with this test procedure,materials so investigated are rated either V-O, V-I or V-II based on theresults of 5 specimens. The criteria for each V (for vertical) ratingper UL-94 is briefly as follows:

"V-O": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 5 seconds and none of the specimens shall dripflaming particles which ignite absorbent cotton.

"V-I": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 25 seconds and the glowing does not travelvertically for more than 1/8 inch of the specimen after flaming ceasesand glowing is incapable of igniting absorbent cotton.

"V-II": Average flaming and/or glowing after removal of the ignitingflame shall not exceed 25 seconds and the specimens drip flamingparticles which ignite absorbent cotton.

In addition, a test bar which continues to burn for more than 25 secondsafter removal of the igniting flame is classified, not by UL-94, but bythe standards of the instant invention, as "burns". Further, UL-94requires that all test bars in each test group must meet the V typerating to achieve the particular classification. Otherwise, the 5 barsreceive the rating of the worst single bar. For example, if one bar isclassified as V-II and the other four (4) are classified as V-O, thenthe rating for all 5 bars is V-II.

The test squares are tested for light transmission in a Gardner XL10-CDM instrument. The data shows the amount of incident lighttransmitted by the test squares using air as 100% transmission.

The results of the different additives within the scope of the instantinvention are as follows with a control being the aromatic polycarbonateas prepared above without the additive of the type set forth herein.

                                      TABLE 1                                     __________________________________________________________________________                         Light           No. of Drips                                                  Transmission                                                                         Flame Out Time                                                                         Per Five                                                                              UL-94                            Additive (0.10 parts per hundred)                                                                  (%)    Seconds  Test Bars                                                                             Rating                           __________________________________________________________________________    CONTROL              86     26       13      Burning                          Dipotassium tetrachlorohydroquinone-                                                               80     4.2      0       V-O                              bis(4-chlorophenyl)ether-3,3'-                                                disulfonate                                                                   Potassium 4-bromodiphenylether-                                                                    80     3.6      0       V-O                              4'-sulfonate                                                                  Polysodium poly(2,6-dimethylphenylene-                                                             72     5.2      0       V-I                              oxide)polysulfonate                                                           __________________________________________________________________________

EXAMPLE II

This Example is set forth to demonstrate the effect of the additives ofthis invention at limits of 0.50 parts per hundred parts of thepolycarbonate.

In preparing the test specimens for this Example, 100.00 parts of thepolycarbonate of Example I is mixed with 0.50 parts of the additivelisted in TABLE 2 employing the same procedure. Test specimens are thenmolded using the same procedure employed in Example I. The testspecimens are subjected to the same test procedure of Example I with thefollowing results:

                  TABLE 2                                                         ______________________________________                                                     Light    Flame  No.                                              Additive     Trans-   Out    of Drips                                         (0.50 Parts  mission  Time   Per Five UL-94                                   per hundred  (%)      Seconds                                                                              Test Bars                                                                              Rating                                  ______________________________________                                        CONTROL      86       26       13     Burning                                 Disodium     76       3.8      0      V-0                                     tetrachlorodiphenyl                                                           ether                                                                         disulfonate                                                                   ______________________________________                                    

EXAMPLE III

This Example is set forth to show the effect of a known commerciallyavailable flame retardant additive.

Example I is repeated except that in place of the additives employedtherein, only 1 part decabromodiphenyl ether is used herein. The resultsobtained upon evaluating 5 test bars are the same as obtained for theControl shown in TABLE 1 above.

In the practice of this invention, aromatic carbonate polymers arerendered flame retardant by the addition of certain particular additiveswhich are the metal salts of substituted and unsubstituted sulfonicacids of aromatic ethers and which includes mixtures of these additivesof substituted and unsubstituted sulfonic acids of aromatic ethers aswell as mixtures of the metal salts. The amount of the additivesemployed in the practice of this invention may vary from 0.001 to up toabout 2.0 weight percent.

As indicated previously, the additive of the instant invention comprisesthe alkali or alkali earth metal salts of the substituted andunsubstituted sulfonic acids of aromatic ethers. While a great number ofsuch salts are set forth in the tables of the Examples of the instantinvention, these are only a representative sample of the additive ofthis invention. The sodium, calcium, magnesium, potassium, strontium,lithium, barium, rubidium and cesium salts of other aromatic sulfonicacids can be employed in place of those in the Examples with the sameeffective flame retardancy being achieved. These other salts of aromaticether sulfonic acids are:

calcium 4,4'-dibromodiphenylether-2-sulfonate

potassium 2,5-dimethoxy-3,6-dichlorobenzenesulfonate

sodium 2,5-bis(pentachlorophenoxy)benzenesulfonate

tetrasodium 4,4'-dichlorodiphenylether-2,2',6,6'-tetrasulfonate

polysodium poly(1,3-phenyleneoxide)polysulfonate

polysodium poly(1,4-phenyleneoxide)polysulfonate

polypotassium poly(2,6-diphenylphenyleneoxide) polysulfonate

polycalcium poly(2,6-dichlorophenyleneoxide) polysulfonate

polylithium poly(2-fluoro-6-butylphenyleneoxide) polysulfonate

polysodium poly(2-bromo-6-phenylphenyleneoxide) polysulfonate

In the practice of this invention, the additive is generally prepared bywell known methods in the art. For example, one such well known methodinvolves taking an aromatic ether such as diphenylether and contactingit with either of the electron withdrawing components such as throughchlorination, bromination or nitration. This is then subjected tosulfonation using either sulfuric acid, chlorosulfonic acid, fumingsulfonic acid or sulfur trioxide. These reactions can be carried out atroom temperature or at elevated temperatures such as about 50° C.Alternatively, the order of the above reaction can be reversed. The saltis then prepared by adding the proper alkaline reagent in sufficientamount to make the neutral salt. The salt is then recovered byprecipitation or by distillation of the solvent.

In the case of the trihalomethyl electron withdrawing substituent, suchas trifluoromethyl electron withdrawing substituent, it is best to startwith the prepared trifluoromethyl aromatic ether and then sulfonate asabove, as well as preparing the salt thereof.

In the case of the cyano-substituent, it is best to prepare the sulfonicacid by oxidation of the corresponding thiophenol by hydrogen peroxideor organic peracids. The salt is then made as above and recoveredaccordingly. This technique is also best for the preparation of sulfonicacids with the trichloromethyl substituent.

In the practice of this invention, any of the aromatic polycarbonatescan be employed herein having a refractive index in the range of 1.54 to1.65. These are homopolymers and copolymers and mixtures thereof thatare prepared by reacting a dihydric phenol with a carbonate precursor.Typical of some of the dihydric phenols that may be employed in thepractice of this invention are bisphenol-A,(2,2-bis(4-hydroxyphenyl)propane), bis(4-hydroxyphenyl) methane,2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-bis(4-hydroxyphenyl)heptane, 2,2-(3,5,3',5'-tetrachloro-4,4'-dihydroxydiphenyl)propane,2,2-(3,5,3',5'-tetrabromo-4,4'-dihydroxydiphenyl)propane,(3,3'-dichloro-4,4'-dihydroxyphenyl)methane. Other dihydric phenols ofthe bisphenol type are also available and are disclosed in U.S. Pat.Nos. 2,999,835, 3,028,365 and 3,334,154.

It is, of course, possible to employ two or more different dihydricphenols or a copolymer of a dihydric phenol with a glycol or withhydroxy or acid terminated polyester, or with a dibasic acid in theevent a carbonate copolymer or interpolymer rather than a homopolymer isdesired for use in the preparation of the aromatic carbonate polymers ofthis invention. Also employed in the practice of this invention may beblends of any of the above materials to provide the aromatic carbonatepolymer.

The carbonate precursor may be either a carbonyl halide, a carbonateester or a haloformate. The carbonyl halides which can be employedherein are carbonyl bromide, carbonyl chloride and mixtures thereof.Typical of the carbonate esters which may be employed herein arediphenyl carbonate, di-(halophenyl)carbonates such as di-(chlorophenyl)carbonate, di-(bromophenyl) carbonate, di-(trichlorophenyl) carbonate,di-(tribromophenyl) carbonates, etc., di-(alkylphenyl) carbonates suchas di(tolyl) carbonate, etc., di-(naphthyl) carbonate,di-(chloronaphthyl) carbonate, phenyl tolyl carbonate, chlorophenylchloronaphthyl carbonate, etc., or mixtures thereof. The haloformatessuitable for use herein include bis-haloformates of dihydric phenols(bischloroformates of hydroquinone, etc.) or glycols (bishaloformates ofethylene glycol, neopentyl glycol, polyethylene glycol, etc.). Whileother carbonate precursors will occur to those skilled in the art,carbonyl chloride, also known as phosgene, is preferred.

Also included are the polymeric derivatives of a dihydric phenol, adicarboxylic acid and carbonic acid. These are disclosed in U.S. Pat.No. 3,169,121 which is incorporated herein by reference.

The aromatic carbonate polymers of this invention may be prepared byemploying a molecular weight regulator, an acid acceptor and a catalyst.The molecular weight regulators which can be employed in carrying outthe process of this invention include monohydric phenols such as phenol,chroman-I, paratertiarybutylphenol, parabromophenol, primary andsecondary amines, etc. Preferably, phenol is employed as the molecularweight regulator.

A suitable acid acceptor may be either an organic or an inorganic acidacceptor. A suitable organic acid acceptor is a tertiary amine andincludes such materials as pyridine, triethylamine, dimethylaniline,tributylamine, etc. The inorganic acid acceptor may be one which can beeither a hydroxide, a carbonate, a bicarbonate, or a phosphate of analkali or alkaline earth metal.

The catalysts which are employed herein can be any of the suitablecatalysts that aid the polymerization of bisphenol-A with phosgene.Suitable catalysts include tertiary amines such as, for example,triethylamine, tripropylamine, N,N-dimethylaniline, quaternary ammoniumcompounds such as, for example, tetraethylammonium bromide, cetyltriethyl ammonium bromide, tetra-n-heptylammonium iodide, tetra-n-propylammonium bromide, tetramethylammonium chloride, tetramethyl ammoniumhydroxide, tetra-n-butyl ammonium iodide, benzyltrimethyl ammoniumchloride and quaternary phosphonium compounds such as, for example,n-butyltriphenyl phosphonium bromide and methyltriphenyl phosphoniumbromide.

Also, included herein are branched polycarbonates wherein apolyfunctional aromatic compound is reacted with the dihydric phenol andcarbonate precursor to provide a thermoplastic randomly branchedpolycarbonate.

These polyfunctional aromatic compounds contain at least threefunctional groups which are carboxyl, carboxylic anhydride, haloformylor mixtures thereof. Examples of these polyfunctional aromatic compoundswhich may be employed in the practice of this invention include:trimellitic anhydride, trimellitic acid, trimellityl trichloride,4-chloroformyl phthalic anhydride, pyromellitic acid, pyromelliticdianhydride, mellitic acid, mellitic anhydride, trimesic acid,benzophenonetetracarboxylic acid, benzophenonetetracarboxylic anhydrideand the like. The preferred polyfunctional aromatic compounds aretrimellitic anhydride or trimellitic acid or their haloformylderivatives.

Also, included herein are blends of a linear polycarbonate and abranched polycarbonate.

It will thus be seen that the objects set forth above among those madeapparent from the preceding description are efficiently attained andsince certain changes may be made in carrying out the above process andin the composition set forth without departing from the scope of thisinvention, it is intended that all matters contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:
 1. In a flame retardant aromatic carbonate polymer composition comprising in admixture an aromatic carbonate polymer and an additive selected from the group consisting of the metal salts of substituted and unsubstituted sulfonic acids of monomeric and polymeric aromatic ethers and mixtures thereof, wherein said metal salts are selected from the group consisting of alkali metals and alkaline earth metals, and mixtures of these metal salts, and said substituent on the metal salt of the substituted sulfonic acids of aromatic ethers is selected from the group consisting of alkyl, aryl, alkoxy, and aryloxy of 1 to 12 carbon atoms and electron withdrawing radicals and mixtures thereof; the improvement comprising including said additive in said admixture in an amount of from 0.001 to about 2.0 parts per hundred parts of the aromatic carbonate polymer, said aromatic carbonate polymer and said additive each having a refractive index in the range of 1.54 to 1.65 such that said composition is non-opaque.
 2. In a shaped article comprising in admixture an aromatic carbonate polymer and an additive selected from the group consisting of the metal salts of substituted and unsubstituted sulfonic acids of monomeric and polymeric aromatic ethers and mixtures thereof, wherein said metal salts are selected from the group consisting of alkali metals and alkaline earth metals, and mixtures of these metal salts, and said substituent on the metal salt of the substituted sulfonic acids of aromatic ethers is selected from the group consisting of alkyl, aryl, alkoxy and aryloxy of 1 to 12 carbon atoms and electron withdrawing radicals and mixtures thereof, the improvement comprising including said additive in said admixture in an amount of from 0.001 to about 2.0 parts per hundred parts of said aromatic carbonate polymer, said additive and said aromatic carbonate polymer each having a refractive index in the range of 1.54 to 1.65 such that said article has a refractive index in the range of 1.54 to 1.65 and is non-opaque.
 3. The shaped article of claim 2 wherein the metal salt of the substituted and unsubstituted sulfonic acids of aromatic ethers have the following formula:

    R'--O.sub.1-2 --R"(SO.sub.3 M).sub.1-6 (X).sub.0-11

wherein R' and R" are independently selected from the group consisting or aryl radicals of 1-2 aromatic rings and an aliphatic radical of 1-6 carbon atoms, provided, however, that R' and R" must contain at least one aromatic radical, and wherein M is a metal selected from the group consisting of alkali metals and alkaline earth metals and X is selected from the group consisting of alkyl, aryl, alkoxy, aryloxy of 1 to 12 carbon atoms and an electron withdrawing radical and mixtures thereof.
 4. The shaped article of claim 3 wherein the electron withdrawing radical is selected from the group consisting of halo-, nitro-, trihalomethyl- and cyano- radicals and mixtures thereof.
 5. The shaped article of claim 2 wherein X is chlorine.
 6. The shaped article of claim 2 wherein R' and R" are aryl radicals of one aromatic ring each.
 7. The shaped article of claim 2 wherein M is calcium.
 8. The shaped article of claim 2 wherein the metal salt has the following formula: ##STR3##
 9. The shaped article of claim 2 wherein the metal salt is dipotassium tetrachlorohydroquinone-bis(4-chlorophenyl) ether-3,3'-disulfonate.
 10. The shaped article of claim 2 wherein the metal salt is disodium tetrachlorodiphenylether disulfonate.
 11. The shaped article of claim 2 wherein the metal salt of the unsubstituted and substituted sulfonic acids of polymeric aromatic ethers have the following formula:

    [A].sub.x [B].sub.y [ArO].sub.n [X].sub.s [SO.sub.3 M].sub.t H

wherein Ar is a phenylene radical, O is oxygen, A is an alkyl radical of 1-4 carbon atoms, B is a phenyl radical, X is selected from fluorine, chlorine and bromine, alkyl, aryl, alkoxy and aryloxy of 1 to 12 carbon atoms, M is a metal which may be selected from the periodic table of either an alkali metal or an alkali earth metal, n is an integer of from 2 to 300, x, y and s are integers of from 0-600 and t is an integer of from 1-600.
 12. The shaped article of claim 11 wherein X is chlorine.
 13. The shaped article of claim 11 wherein A is methyl.
 14. The shaped article of claim 11 wherein M is sodium.
 15. The composition of claim 11 wherein the composition is polysodium poly(2,6-dimethylphenyleneoxide)polysulfonate.
 16. The shaped article of claim 2 in the form of a sheet.
 17. The shaped article of claim 2 in the form of a pellet. 